DE102004034708A1 - Process for the batch production of polymers by melt condensation - Google Patents

Abstract

Disclosed are a method and a device for batchwise production of high-molecular polyphosphonates, polysulfones, polyarylates, polyamides, polyarylene ethers, or polyether ketones by melt-condensing a monomer compound carrying hydroxyl groups, carboxyl groups, anhydride groups, phosphoric acid groups, phosphono groups, phosphonate groups, phosphino groups, phosphinate groups, carbonyl groups, sulfonyl groups, sulfonate groups, siloxane groups or amino groups on its own or along with at least one diphenol, dialcohol, diamine, or a dicarbonate component. According to the invention, a) esterification or reesterification and precondensation are performed in a batchwise operated first reactor ( 1 ) in the presence of an esterification catalyst or reesterification catalyst; b) polycondensation is then optionally performed in a batchwise operated intermediate reactor ( 6 ) by optionally adding one or several additional monomers, another catalyst, and additives until a predetermined polycondensation level or viscosity level has been attained; and finally (c) condensation is continued in a batchwise operated final reactor ( 12 ) until the desired polycondensation level or viscosity level has been reached; and d) branching molecules comprising more than two functional groups are optionally added prior to or during esterification or reesterification, prior to or during polycondensation optionally performed in the intermediate reactor, or prior to or during polycondensation performed in the final reactor. The dwell time in the reactors ranges between 5 minutes and 15 hours while the temperature is set to 180 to 300° C. in reactors ( 1 ) and ( 6 ) and to 240 to 400° C. in reactor ( 12 ), the pressure being continuously or gradually lowered from 2000 to 100 mbar in reactors ( 1 ) and ( 6 ) and to 100 to 0.01 mbar in reactor ( 12 ) by sucking off the vapors produced during condensation.

Description

object The invention relates to a process for the batch production of high molecular weight polyphosphonates, polysulfones, polyarylates, polyamides, Polyarylene ethers or polyether ketones by melt condensation a hydroxyl, carboxyl, anhydride, phosphoric, phosphono, phosphonate, Phosphino, phosphinate, carbonyl, sulfonyl, sulfonate, siloxane or amino groups bearing monomeric compound with itself or with at least one diphenol, dialcohol, diamine or a Dicarbonate.

The Invention also relates a process for the preparation of polymers and copolymers with long and / or short-chain single or multiple branches, the star-shaped, comb-like, shrubby, tree-like or dendrimer-shaped branching structures in regular or statistical distribution.

In the from the DE 3 111 653 known processes for the preparation of polyphosphonates are according to regulations and procedures, as are common on a laboratory scale, produced from dihydroxy-diphenyl or other bisphenols or phenyl esters of methylphosphonic in several stepwise process steps polyphosphonates. Examples of other lab-scale polymers are found in D. Braun, H. Cherdron, H. Ritter "Praktikum der Makromolekularen Stoffe", Wiley-VCH Verlag, Weinheim, 1999. In these publications, laboratory-scale distillations and processes are carried out under pressure reduction with simultaneous These processes involve significant costs and effort, which are portable only on a laboratory scale, with a favorable ratio of volume to wall area and thus very good heat transfer rates, which are practically never achieved in a technical apparatus For example, the volume increases with the cube of the radius, while the wall surface increases only with the square of the radius, for example, the ratio of volume to wall area for a half-filled 1 L round bottomed flask is 1.9 and for a half-filled one 2000 l spherical container 2.6 either longer residence times accepted or compensated by heat transfer internals area losses. If fission products are also released during the reaction, which must diffuse out of the reaction mass, the area in this case also decreases in relation to the volume. This leads either to longer residence times or to the incorporation of elements such as stirrers, which cause a strong circulation of the reaction volume.

It is therefore understandable that the transmission one on a laboratory scale conducted Procedure on technical production equipment usually not directly can be done and changes become imperative in the course of the procedure. In many cases, in particular in the production of polymers, it can not be accepted be, with longer Dwell time to work, as it then at the commonly used high Temperatures to decomposition and degradation reaction of the polymer comes.

It therefore set itself the task of the disadvantages mentioned above thereby avoiding the expiration of the procedure and the construction of the therefor used apparatus are coordinated so that it does not come to decomposition and degradation reactions of the polymer. The inventive method is characterized by the fact that with short residence times under vacuum, the produced by melt condensation of monomers Polymers virtually no discoloration and have no gel content. This is achieved by that in a multi-step process first at low temperatures under low thermal load a precondensate is generated, then at higher Temperatures in special reactors of a poly- and final condensation is subjected.

It has been shown that in the batch operated pre-condensation and in terms of sales and range of proven melting tanks or stirred tank cascades for high viscosity Products are not the optimal solution represent. To be considered is also that at very large Reaction volumes hampered the effectiveness of the stirrer and the circulating flow Built-ins also have a significant impact on distribution have the monomers and the polycondensates in the reaction space. at Polymerizations prone to side reactions, in particular the color quality worsen, is too long a stay in poorly flown reactors and harmful to heat exchange surfaces. is the residence time at such sites too long, especially occurs Polycondensation reactions in competition with chain growth Degradation on the polymer chains.

The Most plastics have the unpleasant property, in case of fire to melt and drain.

These disadvantages can be avoided by the incorporation of branching molecules in the polymer chain and in the branches. By adding branching agents, the rheological properties can be changed such that dripping can no longer take place under the influence of heat.

In addition, let by the number and type of branch points comb, shrub, and / or star-like polymer scaffolds generate special properties that adhere to it. So are in particular few long-chain branches suitable, the rheological recovery in the Film bubbles, also referred to as onion formation, to this effect favorable influence that particularly thin and stable films take off or extrude web glass plates.

Of the Invention is based on the object polyphosphonates, polysulfones, Polyarylates, polyamides, polyarylene ethers or polyether ketones with preferably uniform and narrow molecular weight distribution by melt condensation to create. The resulting products should not contain black particles, at the most a very slight yellowing and despite long- or short-chain branches virtually none Have gel content.

• a) in einem absatzweise betriebenen ersten Reaktor 1 in Gegenwart eines Veresterungs- und Umesterungskatalysators eine Veresterung oder Umesterung sowie eine Vorkondensation durchführt;
• b) dann in einem absatzweise betriebenen Zwischenreaktor 6, ggf. unter Zugabe eines oder mehrerer weiterer Monomerer, eines weiteren Katalysators und Additiven eine Polykondensation bis zum Erreichen eines vorbestimmten Polykondensations- oder Viskositätsgrades vornimmt und schließlich
• c) in einem absatzweise betriebenen Endreaktor 12 die Kondensation bis zum Erreichen des gewünschten Polykondensations- oder Viskositätsgrades fortsetzt und gegebenenfalls Verzweigermoleküle, die mehr als zwei funktionelle Gruppen aufweisen, • vor oder während der Veresterung oder Umesterung im Reaktor 1, • vor oder während der Polykondensation im Zwischenreaktor 6 oder • vor oder während der Polykondensation im Endreaktor 12 zusetzt,

wobei man eine Verweilzeit in den Reaktoren zwischen 5 Minuten und 15 Stunden einhält, die Temperatur in den Reaktoren 1 und 6 auf 180 bis 300°C und im Reaktor 12 auf 240 bis 400°C einstellt und unter Absaugen der bei der Kondensation entstehenden Dämpfe den Druck im Reaktor 1 und im Zwischenreaktor 6 im Lauf der Verweilzeit kontinuierlich von 2000 bis auf 100 mbar und im Endreaktor 12 von 100 bis auf 0,01 mbar absenkt.This object is achieved by a process for the batchwise preparation of high molecular weight polyphosphonates, polysulfones, polyarylates, polyamides, polyarylene ethers or polyether ketones by melt condensation of a hydroxyl, carboxyl, anhydride, phosphoric, phosphono, phosphonate, phosphino, phosphinate, Carbonyl, sulfonyl, sulfonate, siloxane or amino-containing monomeric compound with itself or with at least one diphenol, dialcohol, diamine or a Dicarbonatkomponente in which

• a) in a batchwise operated first reactor 1 in the presence of an esterification and transesterification catalyst performs an esterification or transesterification and a precondensation;
• b) then in a batchwise operated intermediate reactor 6 , optionally with the addition of one or more further monomers, a further catalyst and additives performs a polycondensation until reaching a predetermined degree of polycondensation or viscosity and finally
• c) in a batchwise operated end reactor 12 the condensation continues until the desired degree of polycondensation or viscosity has been reached and optionally branching molecules which have more than two functional groups, before or during the esterification or transesterification in the reactor 1 , • before or during the polycondensation in the intermediate reactor 6 or • before or during polycondensation in the final reactor 12 adding,

maintaining a residence time in the reactors between 5 minutes and 15 hours, the temperature in the reactors 1 and 6 at 180 to 300 ° C and in the reactor 12 adjusted to 240 to 400 ° C and under suction of the resulting vapors in the condensation, the pressure in the reactor 1 and in the intermediate reactor 6 in the course of the residence time continuously from 2000 to 100 mbar and in the final reactor 12 lowered from 100 to 0.01 mbar.

Under the given conditions arise in the intermediate reactor 6 especially shrubby long- and short-chain branches, while in the final reactor 12 statistical and comb-like branches are formed.

This method is exemplified by the 1 . 2 and 3 shown.

In this case, one conveys the monomer or monomers intermittently via filling locks under inert atmosphere in monomer templates (not shown in the figures). From these templates are then predetermined, determined by the amount of batch-produced polymer certain masses, as far as they are present at ambient temperature as a solid, as powdered monomers in the first reactor 1 fed. At ambient temperature liquid present monomers get from inertized templates by means of gas-tight conveying elements in the reactor 1 , Depending on the volatility of the monomers at the desired reaction conditions, the equimolar molar ratio of 1: 1 exceeding metering of the monomers is made. In order to maintain constant the concentration of the monomers escaping during the reaction together with the cleavage products, the vapors of a rectification column 4 fed. The operation of this column is conducted so that the less volatile monomers collect in the sump and the reactor 1 be forwarded again. The more volatile fission products reach the top of the column 4 , be in the condenser 5 knocked down and as a partial stream of the column 4 fed back as reflux. The reflux ratio is dependent on the effectiveness of the separation of the monomer by the column 4 , Of course, with increasing conversion in a batch mode, the mole ratios of cleavage product and monomer in the vapors will change, so that the operating conditions must follow these conditions.

In the esterification and / or transesterification stage in the reactor 1 At higher temperature and in the presence of a suitable catalyst, the first reaction takes place. The esterification or transesterification product obtained from this reactor is according to 1 through the pump 2 and the valve 3 so long in a circle, until a fixed dwell time is reached and the product by switching the valve 3 the intermediate reactor 6 can be supplied, where other monomers, for example those monomers having tri-, tetra- and / or higher functional groups, all at once or can be added successively. In this case, according to the invention, the constantly changing properties of the pump 7 and the valve 8th flowing product, for example, by continuous measurement of rheological properties according to the German patent application DE 102 00 228 , the change of the pressure wave behavior according to the German patent application DE 103 47 826 or the change in the spectroscopic properties by the method of known FTIR, NIR-UV spectroscopy monitored. In this case, the addition of the modifying monomers is controlled particularly advantageously by continuous monitoring of the properties of the polycondensate.

The additional cleavage products released during this subsequent and / or subsequent reaction with the prereacted product also still contain proportions of the added monomers. In order to ensure an economic use of these usually very expensive products and not having to recover them from a strong dilution with the cleavage products, the vapors of a rectification column 9 fed. The operation of the column 9 is conducted so that the less volatile monomers collect in the sump and the reactor 9 be forwarded again. The more volatile fission products reach the top of the column 9 , be in the condenser 10 knocked down and as a partial stream of the column 9 returned to the return. The reflux ratio, determined by the part of the product after 9 to the part of the sump 16 is dependent on the effectiveness of the deposition of the monomer through the column 9 , Of course, with increasing conversion in a batch operation, the mole ratios of cleavage product and monomer in the vapors will change and the operating conditions must follow these conditions.

The polymer obtained from this reactor passes according to 1 over the valves 8th and 11 to the polycondensation reactor 12 , a specially designed final reactor, as described for example in European Patent Application 1 251 957. This reactor has a substantially horizontally driven shaft with attached stirring elements, of which the polyphosphonate, polyarylate, polysulfonate or polyether ketone and their copolymers by means of the gear pump 13 from the final reactor 12 subtracted from. The precondensate is polycondensed in the final reactor at a melt residence time of 5 minutes to 15 hours and preferably 15 to 600 minutes. The temperatures are kept in the reactor 1 and / or in the intermediate reactor 6 in the range between 180 and 300 ° C, while in the final reactor 12 be raised to the range of 240 to 400 ° C. It sucks by means of steam jet and / or mechanical blower 17 from each reactor from the liberated in the reaction vapors and lowers the pressure in the esterification and / or transesterification reactor 1 as well as in the intermediate reactor 6 continuously or stepwise from 2000 to 100 mbar and in the final reactor to 100 to 0.1 mbar. It has proved to be particularly advantageous in the reactor 1 the pressure only after reaching the complete transesterification and a first precondensation with chain repeating units up to 20 structural units to lower the pressure slowly linearly or in stages. By this measure, the formation of large gas bubbles can prevent, which would lead to the bursting that would be entrained by the gas or fission product vapor stream polymer particles.

This in 2 illustrated method concept is particularly advantageous if costs for the equipment are to be kept low. The preparation of the abovementioned polymers is hereby achieved by conveying the monomers batchwise via filler locks from monomer supports (not shown) under an inert atmosphere. From these templates are then given predetermined masses, which are determined by the amount of produce the polymer in the first reactor 1 fed. When the monomers are solid at ambient temperature, they are introduced in powder form. If they are liquid at ambient temperature, the monomers are made from inertized templates by means of gas-tight conveying elements in the reactor 1 brought in. Depending on the volatility of the monomers at the desired reaction conditions, a monomer dosage exceeding the equimolar molar ratio of 1: 1 is carried out.

Deviating from the case of 1 Here, no rectification of the escaping during the reaction with the cleavage products monomers takes place here. The vapors escaping from the reactor become in the condenser 19 knocked down and the condensate collector 16 fed.

In the esterification and / or transesterification stage in the reactor 1 takes place at higher temperature and with addition of catalyst, the first reaction takes place. The esterification or transesterification product obtained in this way is according to 2 through the pump 2 and the valve 3 circulated until a specified viscosity is reached, and then the product by switching the valve 3 the final reactor 12 fed. The addition of further monomers, for example those having tri-, tetra- and / or higher functional groups takes place at once or one after the other in the circulation line to the reactor 1 , In this case, according to the invention, the constantly changing properties of the pump 2 and the valve 3 pumped product, for example, by continuous measurement of the rheological properties according to the DE 102 00 228 , the change in the pressure wave behavior according to DE 103 47 826 or the change in optical properties monitored by the method of known FTIR, NIR or UV spectroscopy. The addition of the modifying monomers is particularly advantageously carried out as a function of a control of the properties of the condensate.

The additional cleavage products released during this post- and / or subsequent reaction with the prereacted product are also condensed and contained in the container 16 collected. That from the reactor 1 obtained polymers according to 2 over the valves 3 and 11 to the final polycondensation reactor 12 , a specially designed final reactor, such as in the EP 1 251 957 is described. These reactors have a substantially horizontally driven shaft and stirring elements attached thereto, the obtained polycondensate having a gear pump 13 is withdrawn from the final reactor. At the same time the valve becomes 14 adjusted so that the polycondensate over the valve 14 to the reactor 12 is returned until the desired degree of polycondensation is reached. After reaching the end of the polycondensation, the valve 14 switched so that the final product by means of pump 13 to the granulator 18 is conducted and cut there to deterrence to Polymerschnitzeln.

The from the reactor 12 extracted vapors are in the condenser 21 knocked down and in the container 16 collected. After completion of the production of the respective batch, the entire condensate is pumped 23 for distillation and rectification 24 driven, where first the more volatile products are expelled overhead. In this case, the operation of the column 24 managed so that the less volatile monomers collect in the sump and in the containers 28 . 29 . 30 be caught. The more volatile fission products reach the top of the column 24 , be in the condenser 25 knocked down and as a partial stream of the column 24 in the return over the valve 35 fed back to the process. The reflux ratio, determined by the part of the product after 24 to the part of the collection containers 26 . 27 over valve 34 . 35 is supplied depends on the effectiveness and the substance to be rectified.

Deviating from the case of 1 and 2 described method finds in the in 3 a simultaneous rectification of the monomers escaping during the reaction together with the cleavage products instead. These escape from the reactor 1 as vapors and become the column 4 supplied, wherein the higher than the cleavage products boiling monomers deposited and as a bottom product in the reactor 1 to be led back. The overhead low boilers or fission products are tor in the capaci 5 condensed. The condensate is divided into the column return and the product to be discharged, which is the condensate collector 16 is supplied.

In the esterification and / or transesterification stage in the reactor 1 takes place at higher temperature and with the addition of catalyst 1 the first reaction of monomers A and B takes place. The esterification or transesterification product from A and B obtained in this way is determined according to 3 through the pump 2 and the valve 3 circulated until a specified viscosity is reached. Thereafter, by switching the valve 3 the feed to the final reactor 12 , The addition of further monomers, for example those having tri-, tetra- and / or higher functional groups takes place all at once or in succession in the circulation line to the reactor 1 , In this case, according to the invention, the constantly changing properties of the pump 2 and the valve 3 pumped product, for example, by continuous measurement of the rheological properties according to the DE 102 00 228 , the change in the pressure wave behavior according to DE 103 47 826 or the change in optical properties monitored by the method of known FTIR, NIR or UV spectroscopy. It is particularly advantageous to add the modifying monomer C and / or optionally a further catalyst II as a function of a control of the properties of the condensate.

The additional cleavage products released during this subsequent and / or subsequent reaction with the prereacted product become rectification 4 fed to the separation of monomers. That from the reactor 1 obtained polymers according to 3 over the valves 3 and 11 to the final polycondensation reactor 12 , a specially designed final reactor, such as in the EP 1 251 957 is described. This reactor has a substantially horizontally driven shaft and attached thereto stirring elements, wherein the resulting polycondensate with a gear pump 13 is withdrawn from the final reactor. At the same time the valve becomes 14 adjusted so that the polycondensate over the valve 14 to the reactor 12 is returned until the desired degree of polycondensation is reached. After reaching the end of the polycondensation, the valve 14 switched so that the final product by means of pump 13 to the granulator 18 is conducted and cut there to deterrence to Polymerschnitzeln.

The from the reactor 12 extracted vapors are in the condenser 21 dejected and in the container 16 collected. After completion of the production of the respective batch, the entire condensate from 16 by pump 23 during the next batch for distillation and rectification 4 driven, where the more volatile products are driven out of the head. In this case, the operation of the column 4 conducted so that the less volatile monomers collect in the sump and in the reactor 1 be returned. The more volatile fission products reach the top of the column 4 , be in the condenser 5 knocked down and as a partial stream of the column 4 as return over the valve 35 fed. The reflux ratio, depending on the type and construction of the column internals and the substance to be rectified and must be adapted over the time course of the reaction in order to achieve an optimum separation effect.

For the preparation according to the invention for example, polycondensates contain monomeric phosphate components, Dihydroxydiphenyl and other bisphenols and diphenyl esters of methylphosphonic in question. For the Diphenol or dialcohol component are particularly suitable in the trade under the name "bisphenol A to F "known Diphenols, however, can also other diphenols are used.

Suitable transesterification catalysts are organometallic compounds such as zinc acetate or sodium phenolate, which are described, for example, in US Pat DE 31 11 653 and other organometallic compounds which have been proposed by D. Braun, H. Cherdron, H. Ritter in "Praktikum der Makromolekularen Stoffe", Wiley-VCH Verlag, Weinheim, 1999.

Substantial influence on the product properties have in the process according to the invention applied in the various reactors Tem temperatures and pressures. In this case, the quality of the polycondensate obtained according to the invention is decisively influenced by the shape of the reactor, since it depends on it the residence time, the mass transfer, the surface renewal property and the self-cleaning behavior, which determine in a special way the properties of the polycondensate. Stirred vessels or cascades are well suited for the first step, melting, reaching the stoichiometric ratio of monomers, catalyst addition, and incipient reaction. For the subsequent onset of polycondensation, in which with increasing chain growth increasingly viscous products, they are only conditionally suitable and only after installation of special mixing elements and after adjustment of the stirring element to the changing polymer properties. For the continuously changing properties of the product with increasing condensation and increasing chain length are as intermediate reactor or as a final reactor in the EP 1 251 957 described annular disk reactor types and their preferred for the batch mode versions preferred. To promote the outgassing of fission products which are released in the course of esterification, transesterification and polycondensation as the chain extension progresses, the pressure in the individual reactors is steadily reduced. To create a vacuum in the reactors, one may use steam ejectors as described in U.S. Patent No. 5,576,414. It is advisable to ensure that the pressure in a reactor immediately following is at most half as high as in the immediately preceding reactor.

For the preparation of polymers which have a different structure from the skeleton by the addition of another monomer, various processes can be used. An inventively provided process variant provides that during the intermediate reactor 6 Consecutive condensation is added to a further monomer and then in this reactor under changed or same conditions as prevail in the first reactor, the polymerization and / or the grafting reaction is continued, wherein star-shaped, comb-like, bush-like, tree-like and dendrimer-shaped branching structures in regular and random Distribution can be formed. In such a grafting reaction and / or chain branching, in addition to the additional monomer, a further catalyst and stabilizers, flow improvers and solids-containing additives are added which can lead to contamination of the reactor and interfere with subsequent reaction in the same reactor, if complete emptying and purification of the reactor not possible. Such contamination of the monomers in the base polymer batch with the added other substances is for the reactor 1 not advantageous because it can lead to undesirable side reaction and / or other product properties than the desired one.

A three-stage process procedure has the advantage that it is possible to gradually raise the temperature in the downstream reactors and thus also to regulate the vacuum necessary for sucking off the cleavage products and to adapt them to economic considerations. As a result, low initial temperatures can be set at the beginning of the polycondensation with short chains of the molecules and at a still low polymer melting point. Also arise at the beginning of the polycondensation large amounts of fission products and it is advantageous in terms of apparatus and economy to suck them with only a slight negative pressure, which also with cheaper pumps or suction emitters can work. In practice, steam or liquid radiators have proved to be particularly reliable for this aspiration, while the operation with mechanical blowers causes high investment costs, but offers the highest energy efficiency. The addition of a branching agent in this phase leads to long-chain branches, which in turn can branch again and thus have dendrimerartige or tree-like structure.

With increasing reaction time and reaction temperature, the polymer chains grow, so that in the intermediate reactor 6 Chain lengths of 15 to 35 structural units and in the final reactor 12 Chain lengths of 30 to 100 structural units can be achieved. The toughness of the melt increases and the design of the polycondensation reactor with special rheological properties becomes necessary. In this case, the interior of such a reactor can deviate from the cylindrical shape and, for example, also have a conical shape. The addition of a branching agent in this phase leads to branchings of short and / or medium length and show a more or less shrubby and / or comb-like structure.

The Invention is explained in more detail by the following examples:

example 1

The supplied as crystallized, powdered or pelletized raw material monomers bisphenol A, also abbreviated as BPA, and diphenylmethylphosphonate, also abbreviated as DPMP, are filled into storage tanks and continuously introduced by means of metering screws in Aufschmelzer equipped with heat exchangers and stirrers. From the two storage containers, the aliquot mass flows of molten monomer determined by the stoichiometry of the reaction are transferred to the transesterification vessel 1 promoted, which is equipped with a Mantelbeheizung and a stirrer. From a template, the addition of known from the polymer literature mixed catalysts consisting of an alkali metal salt of bisphenol and zinc acetate as in the patent DE 31 11 653 described. The reaction of the two monomers is initiated at a temperature of 240 ° C and a pressure of 800 mbar. The liberated phenol is collected to determine the progress of the reaction and determined volumetrically. The transesterified product from the reactor 1 still has a low average polymer chain length, which is an average of 10 repeating units or structural units and still has small amounts of unreacted monomer due to the residence time behavior in the stirred tank. The molecular weight distribution, the residual content of monomers and the average molecular weight of the transesterification product are monitored by chromatography. This product enters the intermediate reactor 6 , which is operated at a pressure of 200 mbar. Here, a continuous heating of 240 to 280 ° C takes place over 2.5 hours. The resulting fission products are from a multi-stage liquid-steam jet system 17 aspirated and after rectification at a temperature which is above the boiling point of the cleavage product and below the boiling point of the monomer contained in the vapors in the condenser 5 beaten down. From the intermediate stage 6 the product enters the final reactor 12 with the help of a pump 7 , where at a pressure of 1.5 mbar, a temperature of 330 ° C and a residence time of 200 minutes, the polycondensation is completed. The increasing chain length or viscosity during the residence time is taken into account by the fact that the rotating disks, annular disks and ring disk segments necessary for the production of the surface are cleaned of statistical elements. HVSR, Kunststoffe 1/1992 pp. 19-20, is particularly suitable for this purpose. That the final reactor 12 leaving product shows only slight yellowing by degradation products extremely low levels of gels and black particles and a narrow molecular weight distribution.

Example 2

In a pilot plant consisting of the reactors in 1 and a procedure as described in Example 1, an esterification step 1 fed from three templates with terephthalic acid, isophthalic acid and bisphenol A in a molar ratio of 1: 0:75: 1.75. From a template, the addition of the catalyst takes place in the form of an alkali metal salt of bisphenol. The reaction of the monomers is initiated at a temperature of 280 ° C and a pressure of 800 mbar. The liberated water is collected to determine the progress of the reaction and determined volumetrically. The esterified product from the reactor 1 arrives analogously to Example 1 in the intermediate reactor 6 , which is operated at a pressure of 250 mbar. Here, the addition of 103 mol per mole of bisphenol diphenylmethylphosphonate and the product undergoes a continuous heating from 280 to 300 ° C at a residence time of 145 minutes. The product condenses on and the resulting cleavage product is sucked off by the multistage liquid steam jet system. From the intermediate reactor 6 the product reaches the end of the reaction time by means of a pump 7 and valve 8th in the final reactor 12 , which is maintained at 25 mbar pressure and in which the temperature is continuously from the exit temperature of the intermediate reactor 6 rises to a temperature of 320 ° C at 60 minutes residence time. From the reactor 12 , where at a pressure of 0.5 mbar, a Tempe temperature of 330 ° C and a residence time of 65 minutes, the polycondensation is completed, the product passes through a gear pump 13 in the granulator 18 , That the granulator 18 leaving product shows only slight yellowing by degradation products extremely low levels of gels and black particles and a narrow molecular weight distribution.

Example 3

In a pilot plant, as described in Example 1, an esterification step 1 fed from three templates with terephthalic acid, isophthalic acid and bisphenol A in a molar ratio of 1: 0:75: 1.75. From a template, the addition of the catalyst takes place in the form of an alkali metal salt of bisphenol A. It is followed by the addition of 10 ^-3 mol per mole of bisphenol to 1,3,5-trihydroxyphenol in the intermediate reactor 6 and continuous heating from 240 to 280 ° C over 2.5 hours.

Example 4

In a pilot plant, as described in Example 1, an esterification step 5 from four templates with terephthalic acid, isophthalic acid, p-phenylenediamine and o-phenylenediamine in a molar ratio of 1: 1: 1.03 1 fed. From a template, the addition of the catalyst takes place in the form of an organo-organic compound. The reaction of the monomers is initiated at a temperature of 180 ° C and a pressure of 1000 mbar.

1

Esterification / transesterification reactor - 1st stage

2

Circulation / transfer pump - 1st stage

3

switching valve Circulation / transfer - 1st stage

4

Rectification column - 1st stage

5

Vapor condenser - 1st stage

6

Intermediate reactor - 2nd stage

7

Circulation / transfer pump - 2nd stage

8th

switching valve Circulation / transfer - 2nd stage

9

rectification column Intermediate level - 2. step

10

vapor condenser Intermediate level - 2. step

11

switching valve Circulation / transfer - power amplifier

12

Polycondensation reactor - final stage

13

gear pump Circulation / discharge - output stage

14

switching valve Circulation / discharge - output stage

15

vapor condenser Polycondensation reactor - final stage

16

Clippings

17

vacuum generating station

18

granulator

19

vapor condenser Esterification / transesterification

20

21

vapor condenser polycondensation

22

Circulation / transfer pump rectification

23

heat exchangers rectification

24

Reaktifikationskolonne

25

vapor condenser rectification

26

Collection container fission product

27

Collection container fission product

28

Collection container monomer A-C

29

Collection container monomer A-C

30

Collection container monomer A-C

31

feed pump Monomer A-C

32

feed pump Monomer A-C

33

feed pump Monomer A-C

34

switching valve Circulation / collecting tank

35

switching valve Circulation / collecting tank

36

switchover Circulation / collecting tank

37

switching valve Circulation / collecting tank

38

switching valve Circulation / collecting tank

M

continuous Measurement, monitoring and control

Claims (13)

Process for the batchwise preparation of high molecular weight polyphosphonates, polysulfones, polyarylates, polyamides, polyarylene ethers or polyether ketones by melt condensation of a hydroxyl, carboxyl, anhydride, phosphoric, phosphono, phosphonate, phosphino, phosphinate, carbonyl, sulfonyl, Sulfonate-, siloxane- or amino-containing monomeric compound with itself or with at least one diphenol, dialcohol, diamine or a dicarbonate component, characterized in that a) in a batchwise operated first reactor ( 1 ) in the presence of an esterification or transesterification catalyst performs an esterification or transesterification and a precondensation; b) then in a batchwise operated intermediate reactor ( 6 ), if appropriate with the addition of one or more further monomers, of a further catalyst and additives, a polycondensation is carried out until a predetermined degree of polycondensation or viscosity is reached, and c) finally in a batchwise operated end reactor ( 12 ) the condensation continues until the desired degree of polycondensation or viscosity is reached, and d) if appropriate, branching molecules which have more than two functional groups, before or during the esterification or transesterification in the reactor 1 , • before or during the polycondensation in the intermediate reactor 6 or • before or during polycondensation in the final reactor 12 maintaining a residence time in the reactors between 5 minutes and 15 hours, the temperature in the reactors ( 1 ) and ( 6 ) at 180 to 300 ° C and in the reactor ( 12 ) to 240 to 400 ° C and under suction created in the condensation the vapors the pressure in the reactors ( 1 ) and ( 6 ) continuously or in stages from 2,000 to 100 mbar and in the reactor ( 12 ) lowered to 100 to 0.01 mbar. Method according to claim 1, characterized in that that from the fission product vapors through fractional condensation and / or distillation recovering monomers and the process again. Process according to claims 1 and 2, characterized that the pressure in the reactors is lowered linearly or stepwise and in an immediately following reactor at most only is half as high as in the immediately preceding reactor. Process according to claims 1 to 3, characterized in that in the reactor ( 1 ), esterified and / or transesterified precondensate has average chain lengths of up to 20 structural units. Process according to claims 1 to 4, characterized in that the from the intermediate reactor ( 6 ) product has average chain lengths of 15 to 35 structural units. Process according to claims 1 to 5, characterized in that the from the final reactor ( 12 ) has average chain lengths of 30 to 100 structural units. Process according to claims 1 to 6, characterized that the course of the condensation reaction by continuous Measurement of the rheological properties, the change of the pressure wave behavior and / or the change the optical properties monitored. Process according to claims 1 to 7, characterized that by adding further monomers, stabilizers, flow improvers and / or Additives the rheological properties of the condensation product controls. Process according to claims 1 to 8, characterized the product in each reactor during each residence time circulating. Device for carrying out the method according to claims 1 to 9, characterized in that at least the final reactor ( 12 ) consists of a horizontally disposed container and this has a diameter to length ratio of 0.5: 1 to 5: 1, preferably from 0.7: 1.3 to 3.1. Device according to claim 10, characterized in that that you provide the pipes with a heating jacket whose Temperature at least 2 ° C and at most 20 ° C above the Melting point of the guided through the conduit product is. Device according to claims 10 and 11, characterized in that the final reactor ( 12 ) is equipped with static elements on the reactor walls for producing thin films and for stripping entrained product on rotating disks. Process according to claims 10 to 12, characterized in that the reactor shaft of the horizontal end reactor ( 12 ) has only one passage through the two-sided lid.